Pulsating hydrocarbon conversion



l.. P. EVANS July 15, 1952 FULSATING HYDROCARBON CONVERSION 2 SHEETS-SHEET l Filed Feb. 11, 1950 July 15, 1952 l.. P. EVANS 2,603,591

PULSATING HYDROCARBON CONVERSION Filed Feb. 11, 1950 S'EETS-Sl-IEET 2 Patented July 15, 1952 PULSATING HYDROCARBON CONVERSIONv Louis'l.y Evans, Woodbury, N. J .,assignorto So,-V

cony-Vaouum: Oil Company, corporationof New York Incorporated-- a 'Application February 11, 1950, serial No. 143,664

3 Claims.k (Cl. 19d-E50) i i Thefi'nvention is directed to a novel method, and

apparatus forthe desirablefhydrocarbons;

It is well knownthat hydrocarbons maybev com. verted, for:y various purposes, ,in

processes.V The "contact massy material is .usually an:V adsorptive-inaterial inf 111e. general nature; of

clayf, l such ias v fullerlsfearth; rifllterecl'ays; 'refined`A andnatural clays,racid1treated= clays, various syn-i theticassociations ofi-alumina andsillca,-;suchas coprecipitatedf4 gels','.fgels .'of .alumina and/or silica,

the presence: of particle-form solid contact masszmaterials. f The. purpose `of: the conversionI may. be cracking kof a f gasoil-lto gasoline,freforming,sdehydrogenation, t destructive hydrogenation,r alkylationpisomerization-polymerization, Vorfother Y conversonor fluid reactants in e the --presence of subdivided solid catalyst orparra ticle-form Amater-lala.: Itisy particularly directedV to the catalytic'conversion of hydrocarbonsin the l presenceofsubdivided-solid catalystto form more;

andmsimilarmaterialsial nyrofv which .may have f added Ivnate'rials;suchf-as.4 various Jmetalli'c oxides',

for-variouscataly-tic .purposes connected withy the conversion 1 contemplated.. For example; .in ,'re. forming hydrocarbons ,earomatizing orl dehydrogenating'catalyst such'as-tirrA chromium Aor alu,,.

minum gels are used, or aluminai/withfmolybdev num; oxide `deposited thereon;y In" 'somein.- stances,-such as, for example,vthe conversion of .gasoil to ethylene,inert,' 'particle-'form solids are used; 'such 'as refractory-materialsl-'mullita Corhartyor evenironvballsf.:

I' '.pac't columns Severalsystemsorfconversi'orr of hydrocarbonsv areknown andpracticed-inY the petroleum art' which 'I use y particle'-forrn'A Y contact masses. l'The most common systemsareLp'opularly .known as the fixed bedv system, their ,fluidi system. and the contact material at-the topof the reactor'anday ,m'oving-bedzsystem 'Each'of theseV methods of Y hydrocarbon:conversionhas inherent advantages overl theother systems andy also inherent disad-v vantages. Forfexamplepinthefixed bed system the hydrocarbons: at conversion conditionsv are passed through`A a bed of "contact material-wherein they are-converted to more desirable hydrocarek bons. `During the conversion, the .activity of Athe catalyst varies as coke, formed during the crackingaoperation, adheresstol-the surface of vthe `contact materiali'.As-the-activity of the contact material varies f during thefconversiom the amount of v-th'ef products --v'ar-lessii'rrl .accordance therewithy The' products'removed from -the reactor are charged to a fractionatingftowerwhere the productsare- 'separated --and "the separated products are Athen--chargedto otherrenery apparatus for further-treatment-. Thev proper operation of-'the fractionator andrelatedfireiinery Iequipment requiresthat theV feed-ftothe -A fractionator be of A fairly uniform compositions Therefore,Y in order tomaintainva fairly-'uniform feed -to the-fractionatorythe prior lartshowslthefuse of several ment, however, of many steps, for examplalireaction, purge,aregeneration;

and purge stepswith'at leastvone reactor; .on stream at all times; and' preferably severalireactors on stream at the same time inoverlapping Although a fairly `uniform feed is sup-` sequence. a plied to the -fractionatingequipment by this pro-- cedure, a great amountof costlyv equipmentl isr required, making this system -un r'ttractive, par.'-

ticularly to the smaller refiner.

In the fluid systempf conversion, contact` material-inpowdered-form is maintained in ebullient motion in reaction ,and` regeneration -vesse'lsnloy passing gases-upwarly'throughthe mass-of .pow-1.V A derrat -suici'entvelocityL A streamfofthe pow-V l der 'is continuouslyI` transportediirom the reactor -v to the regeneratorand a secondfstreamofpow-t y der is transported from the regenerator tothe reactor, therebypermitting the maintenance/of a massof particles-injthe reactor-vofgwhich lthe f averageis partially covered-withcarbonaceous i this system deposits. Anobvious disadvantagerof is the fact that-the vreactor will? contain particles of all degrees of coverage of the particlesby carf bonaceous depositsv from fully covered" to :completely free of deposits; 1 Contact material-inthis condition. converts ai 'sin-allerV percentage ofv the feed-stock to hydrocarbons in thefgasol-inerboile' ing range` than particles completely fremd-m11- bonaceousldeposits,

In the moving bed systemthe-*Acontact `mate-- rial Vls passed downwardly 'as i substantially comthroughl the reaction andregeneration-vessels.- f Elevators-or fluid jlifts are-used to raisethecontaet materiaifromithe bttcm of one column to the top ofthe other column.l rIfhis system provides "a'uniform bed -of deposit-free uniform build up ofthedeposits' onthecontact material vas it passes; downwardly through the--v vessel; Both 'thefluid and moving bed systems providea'continuous conversion` to a substantially uniformly composed-product permitting the fractionating equipment to operate -atmaximum vef-Y iiciency',` but the moving bedrs'ystemhas-theradvantage of greaterconversion -tof gasoline V-boil- Because of lthe continuous. move-' tons of particleform" ing products.`

sol-id material, lthe 'particlesL spall and fracture, causing the formation ofundesirable iines. j'1`hese' iines'cause 1 various` :troubles in A thewsystem -when' l theyT "concentrate infy certain' --reg-ions VFor gea-.- ample, theymaycausean interruption of flow in the contact material feedleg'tothe reactor or cause zones ofunequal pressure in `they reaction. e

vessel whichl causes thefreactants to ,pass through'. one section of themoving bed in greater-quantity than in the remaining sections, which 3in1 turn causes-portions of thecontact'xnaterial bed to'be coveredwitn deposits "at a faster, rate'than the remaining portions;

The' objecty of the 'presents invention; is to,- pros vide apparatus and .a hydrocarbon conversion system which will possess the inherent advantages of the previous systems without possessing their disadvantages. A further object of this invention is to provide a suitable conversion system which is not as expensive as previous systems. A further object of this invention is to provide apparatus and a system which will provide continuously a product of converted hydrocarbons sufficiently uniform Yin composition to maintain fractionating equipment under operation at maximum eciency. These and other objects of this invention will be made apparent by'reference to the attached drawing and following description of the invention; in which,

Figure 1 is a diagrammatic view of a hydrocarbonV converter, partially in section, with related refinery equipment; and in Which,

Figure 2 Vis a diagrammatic view of a hydrocarbon reformer, partially in section, and related conduit connections. Y

Referring to the Figure 1,V a fixed-bed conversion chamber I is shown, partially in section. The chamber comprises a centralsection I I, a top section I2 Vand a bottom section I3. The contact material, in particle form, is retained in the central section II by screens or previous partitions I4, I5. The top andbottom sections I2, I3 are shaped to form suitable fluid introduction and removal manifolds. Y 'Y 1 Y In the operation of the system, the hydrocarbon' charging vvstock,Y .properly prepared for conversion, 'is introducedinto the upper manifold through the conduit I6. The flow of reactants maybe controlled by the valve I'I in the conduit I 6. The'hydrocarbonsj pass downwardly through the bed in contact with the comminuted particleform adsorbent catalyst and are converted thereby to conversion products. Just prior to the time when the hydrocarbon vapors would emerge from the bed of catalyst into the lower manifold region, air is introduced into the lower manifold through the conduit I 8. The air flow may be controlled by the valve I 9. Thevalve I 'I is closed and theYvalve-Z inthe exit conduitY2I from the upper manifold is opened.v The air pressure buildsup in the lower manifold and air enters the bed Vof catalyst in an upward direction forcing the reactant products'upward and out of the rchamber I0 through the exit conduit 2|. Just prior to the time when the air would emerge from the topv of the bed of contact material, the valve I 'I is opened admitting reactant fluids to the upper manifold, and the valve is closed. The valve 22 in the exit conduit 23 from the lower manifold is opened and the valve I 9 in the air inlet conduit I8 is closed. Thus the reactant fluids force the exhaust gases, formed during the regeneration phase of the process, out the exit conduit 23.v Y Y l It is seen thatby proper manipulation of the valves the reactant vapors and air may be made to pulse through the bed during exceedingly short cycles. By this procedure the bed is Ymaintained at a fairly uniform degree of activity or exposure and substantially. completely activated condition at all'times. -The products delivered to the fractionating equipment remain of substantially uniform composition and flow at a continuous intermittent rate.Y Y Y yThere is only slight mixing at the interface between the pulsing -reactant-vaporsand -combustion air, the two fluids being maintained substantiallyseparated by a thin layer of' pulsating stagnant gas. l

.ly into a fractionating column 3D.

* densible gases are removed from the top of the column and heavy ends are removed from the bottom. rIhe gasoline fractions are removed from an intermediate point through the conduit v3l to other renery apparatus for further treatment to produce improved gasoline. The prepared product is then customarily sent to storage such as through the conduit 32 to the storage tanks 33.

Many contacting reactions are endothermic requiring the addition. of heat to maintainthe reaction. The. catalytic conversion of hydrocarbons isV typical ofithis type. Variation inthe temperature' ofthe bed during cracking causesr a shift in the distribution of the products, which has been shown to be undesirable. The combus- Y tion of coke on the catalyst formed during the conversion of the hydrocarbonsis an exothermic reaction. Therefore, in the pulsating system of catalytic conversion,l the heat supplied ,to the catalyst during the'regeneration phase is withdrawn by the reactants during the reaction phase. In many instances there is a-substantial Y balance between' the heat released during-re-V generation and. that absorbed during reaction,

whereby 'a substantially' uniform and constant' temperature is maintained in the reaction chamber I0. In someinstances, however, an excess of heat will be generated during the regeneration phase over that required during theYreaction phase. Heat exchanger tubes 34 are provided through the bedv of contact material through which a suitable cooling fluid, such as liquid so-Y dium nitrate, for-example, may be passed to extract the excess 'heat generated, or in certainA circumstances, a heating fluid may be passed to provide heat to the bed.

As indicated, the valves I'I, I9, 20 and 22 are,

suitably, automatically operated and controlled by a central controller, adapted to appropriately time the sequence of steps. YFor example, in the catalytic conversion of hydrocarbons to compounds boiling in the gasoline range, a complete cycle of operation is' effected approximately every 30 seconds. f The vpressure in the vessel may be at substantially atmospheric pressure or may be under a pressure of about 5-15 p. s. i. g. Other pressures maybe used for other types of conversion. For example,.in reforming in the presence of hydrogen, which may be added with the charge, pressure in the neighborhood of 200-300 p. s. i. g. may be utilized. The temperature of` the bed Vduring normal operation Will be in the neighborhood of V800--1100 F.,; although much higher temperatures may be used in special instances; Y Y Y Referring now to Figure 2, apparatus is shown which vcan be used in areforming process to upgrade gasoline stocks to improve octane and other properties of the hydrocarbons. The outer vessel 40 is a vertically mounted vessel of circular crosssection. Within the vessel 40 are mounted two screens or pervious partitions 4I 42, substantially vertically mounted. The annulus between the screens 4I, 42 is filled with a particle-form catalyst or contact material, suitable for effecting reforming of the hydrocarbons in the presence of hydrogen gas. A mixture of hydrocarbons and hydrogen properly prepared for conversion, in the ratio of about Y1/2- 10 mols of hydrogen gas to 1 jmol of hydrocarbon charge is Aintroduced into the central region 43 through the conduit 44. The

tween reaction and regeneration is eliminated. It

has long been recognized that by using short cycles of reaction and regeneration it might be possible to convert in the presence of the catalyst when it is maintained at its highest activity. Consequently, the steps of reaction, purge. regeneration, purge have each been shortened in an effort toachieve this effect. Y But, experimentation provedthat the duration of the purge steps could notbe successfully reduced below a certain minimum, 'dependent uponsizeof contact bed, catalystdensty. and certain other factors.

Attempts to reduce the purge period below the critical minimum time produced several undesirable eiect's which defeated the purpose of the reduction. For example, the purging of the vapors subsequent to reaction was incomplete and the remaining unremoved hydrocarbons were burned during regeneration, producing increased deposits on the contact material. ISimilarly, incomplete purging of the regeneration gases left combustion supportinggases in the vessel duringV conversion, and hence, a portion of the charge was oxidized by these gases producing additional carbonaceous deposits on the contact material. The eXtra carbon deposited on the contact material made it necessary to lengthen the percentage of the cycle used for regeneration, thereby decreasing the reaction period and hence, decreasing the `yield of products produced by the apparatus. In addition to the loss of product entailed, the requiredlonger regeneration period upset the heat balance by producing materially more heat during regeneration than could be successfully utilized during reaction. Attempts to correct this trouble by reducing the temperature of the feed charged to the reactor were unsuccessful. YIt was found that the cool charge tended to condense initially on the contact material, which resulted in an increased lay down of carbonaceous deposits on the contact material.

By this invention these diiiculties are obviated. The layer of stagnant gas, if maintained in the bed, adequately separates the reaction and regeneration gases. In effect, the reaction gases purge the regeneration gases and vice versa, all the steps being effected concomitantly, permitting the use of very short, pulsating cycles.

Although the invention has been described with particular reference to catalytic conversion and reforming, it is not meant to be restricted to the use of catalytic material. And although particular shapes or reaction vessels'have been described this, alsofis not meant to `be limiting.

What is claimed is:

l'. The method of converting hydrocarbons in the presence of a iixed bed of comminuted solid contact material comprising: introducing reactant hydrocarbons into one side of a bed of contact material, at a pressure which is high enough to force the hydrocarbons to penetrate the bed, stopping the iiow of reactant hydrocarbons to the bed prior to the emergence of reactants from the other side of the bed and starting the flow of combustion supporting gas into said other side of the bed, at a pressure which is high enough to force the combustionY supporting gas to penetrate the bed and drive the reactants back out ofthe bed,

withdrawing the conversion products driven :fromv the bed to a collection zone, stopping the ow of combustion supporting gas just prior to the emergence of said gas from the first side of the bed` and starting the flow of reactants into said iirst side of the bed, at a pressure which is high enough 4 8k to force the reactants drive the combustion gas back out of the bed, withdrawing the combustion gas driven'from the bed to a receiving zone and maintaining the pulsation of gases in the bed suiiiciently short to provide a substantially continuous flow of reactants to said collection zone of Vsubstantially uniform composition.

2. The method of converting hydrocarbons in the presence of a iiXed bed of comminuted solid contact material comprising: introducing reactant hydrocarbons into one side of a bed of contactmaterial, at a pressure which is high enough to force the hydrocarbons to penetrate the bed, stopping the flow of reactants to the bed prior to the emergence of reactants from the other side of the bed and starting the iiow of combustion supporting gas into said other side of the bed, at a pressure which is high enough to force the combustionsupporting gas to penetrate the bed and drive the reaction products back out of the bed, withdrawing the reaction products driven from the bed to a collection zone, stopping the flow of combustion supporting gas just prior to the emergence of said gas fromrthe rst side ofthe bed and starting the flow of reactants into said iirst side of the bed,V at a pressure which is high enough to force the reactants to penetrate the bed and drive the combustion gas back out of the bed, withdrawing the combustion gas driven from the bed to a receiving zone and maintaining the pulsations of gases in the bed between about one every 3 seconds to about one every 300 seconds whereby reaction products of substantially uniform composition are supplied to the collection zone.

3. The method of converting hydrocarbons in the presence of a fixed vbed of granular catalyst comprising: introducing reactant hydrocarbons into one Vside of a bed of contact material, at a pressure which is high enough to force the hydrocarbons to penetrate the bed, stopping the ilow of reactants to the bed prior to the emergence of reactants from the other side of the bed and starting the iiow of combustion supporting gas into said other side of the bed, at a pressure which is high enough to force the combustion supporting gas to penetrate the bed and drive the reaction products back out of the bed, withdrawing the reaction products driven from the bed to a collection zone, stopping the flow of combustion supporting gas just prior to the emergence of said gas from the first side of the bed and starting the flow of reactants into said iirst side of the bed, at a pressure which is high enough to force the reactants to penetrate the bed and drive the LOUIS P. EVANS.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,363,738 Mathers/et al. Nov. 28, 1944 2,472,844 Munday et al. June 14, 1949 2,491,303 Eastman Dec. 13, 1949 to penetrate the bed and 

1. THE METHOD OF CONVERTING HYDROCARBONS IN THE PRESENCE OF A FIXED BED OF COMMINUTED SOLID CONTACT MATERIAL COMPRISING: INTRODUCING REACTANT HYDROCARBONS INTO ONE SIDE OF A BED OF CONTACT MATERIAL, AT A PRESSURE WHICH IS HIGH ENOUGH TO FORCE THE HYDROCARBONS TO PENETRATE THE BED, STOPPING THE FLOW OF REACTANT HYDROCARBONS TO THE BED PRIOR TO THE EMERGENCE OF REACTANTS FROM THE OTHER SIDE OF THE BED AND STARTING THE FLOW OF COMBUSTION SUPPORTING GAS INTO SAID OTHER SIDE OF THE BED, AT A PRESSURE WHICH IS HIGH ENOUGH TO FORCE THE COMBUSTION SUPPORTING GAS TO PENETRATE THE BED AND DRIVE THE REACTANTS BACK OUT OF THE BED, WITHDRAWING THE CONVERSION PRODUCT DRIVEN FROM THE BED TO A COLLECTION ZONE, STOPPING THE FLOW OF COMBUSTION SUPPORTING GAS JUST PRIOR TO THE EMERGENCE OF SAID GAS FROM THE FIRST SIDE OF THE BED AND STARTING THE FLOW OF REACTANTS INTO SAID FIRST SIDE OF THE BED, AT A PRESSURE WHICH IS HIGH ENOUGH TO FORCE THE REACTANTS TO PENETRATE THE BED AND DRIVE THE COMBUSTION GAS BACK OUT OF THE BED, WITHDRAWING THE COMBUSTION GAS DRIVEN FROM THE BED TO A RECEIVING ZONE AND MAINTAINING THE PULSATION OF GASES IN THE BED SUFFICIENTLY SHORT TO PROVIDE A SUBSTANTIALLY CONTINUOUS FLOW OF REACTANTS TO SAID COLLECTION ZONE OF SUBSTANTIALLY UNIFORM COMPOSITION. 